The present invention relates to a process for preventing the redeposition of migrating dyes in wash liquors comprising a peroxide and a manganese catalyst, to manganese catalysts suitable for the process, and to detergent formulations comprising these catalysts.
It is already known that some manganese complexes of the salen type are suitable catalysts for oxidations with peroxygen compounds, especially as part of a washing process. The salen complexes involved are exclusively symmetrical. It has also been described before that certain other manganese complexes possess a pronounced bleaching effect on dirt and dyes in wash liquors.
It has now been found that certain asymmetric manganese complexes of the salen type exhibit a much greater specific action as catalysts for preventing the redisposition of migrating dyes in wash liquors without notably damaging either dye or fibre. Complexes are termed asymmetric when they come about through the reaction of 2 mol of two differently modified salicylaldehydes or o-hydroxyphenyl ketones with 1 mol of ethylenediamine or another modified diamine building block and so possess two differently substituted aromatic radicals.
The present invention therefore provides a process for preventing the redeposition of migrating dyes in a wash liquor, which comprises adding to the wash liquor, which comprises a peroxide-containing detergent, from 0.5 to 150 mg, preferably from 1.5 to 75 mg and, in particular, from 7.5 to 40 mg per liter of wash liquor of one or more compounds of the formula 
in which
n is 0, 1, 2 or 3,
m is 1, 2 or 3,
A is an anion;
Y is a linear or branched alkylene radical of the formula xe2x80x94[C(R5)2]rxe2x80x94, where r is an integer from 1 to 8 and the R5 radicals independently of one another are hydrogen or C1-C4alkyl;
xe2x80x94CXxe2x95x90CXxe2x80x94, in which X is cyano, linear or branched C1-C8alkyl or di(linear or branched C1-C8alkyl)-amino,
xe2x80x94(CH2)qxe2x80x94NR4xe2x80x94(CH2)qxe2x80x94, in which R4 is hydrogen or linear or branched C1-C4alkyl and q is 1, 2, 3 or 4; or
a 1,2-cyclohexylene radical of the formula: 
xe2x80x83or a 1,2-aryl radical of the formula 
xe2x80x83in which R9 is SO3H, CH2OH or CH2NH2,
R and R1 independently of one another are cyano, halogen, OR5 or COOR5, in which R5 is hydrogen or linear or branched C1-C4alkyl, or are nitro, linear or branched C1-C8alkyl, linear or branched, partially fluorinated or perfluorinated C1-C8alkyl, NHR8 or NR6R7 in which R6 and R7 are identical or different and are each linear or branched C1-C12alkyl or in which R6 and R7, together with the nitrogen atom connecting them, form a 5-, 6- or 7-membered ring which may include further heteroatoms, or are linear or branched C1-C8 alkyl-R8, in which R8 is a radical OR5, COOR5 or NR6R7 with the above definitions or is NH2, or are xe2x80x94N⊕R4R6R7, in which R4, R6 and R7 are as defined above,
R2 and R3 independently of one another are hydrogen, linear or branched C1-C4 alkyl or unsubstituted aryl, or aryl substituted by cyano, halogen, OR5 or COOR5, in which R5 is hydrogen or linear or branched C1-C4alkyl, or by nitro, linear or branched C1-C8alkyl, NHR6 or NR6R7 in which R6 and R7 are identical or different and are as defined above, or by linear or branched C1-C8alkyl-R8, in which R8 is a radical OR5, COOR5 or NR6R7 with the above definitions or is NH2, or by xe2x80x94N⊕R4R6R7, in which R4, R6 and R7 are as defined above, with the proviso that R and R1 do not have the same definition if n and m are identical.
In the compounds of the formula (1) in which n is 2 or 3 the radicals R can have the same or different definitions. With respect to the radicals R1 the same applies to compounds of the formula (1) in which m is 2 or 3.
Where Y is a 1,2-cyclohexylene radical it may be present in each of its stereoisomeric cis/trans forms.
Preferably Y is a radical of the formula xe2x80x94(CH2)rxe2x80x94, where r is an integer from 1 to 8, or of the formula xe2x80x94C(R5)2xe2x80x94(CH2)pxe2x80x94C(R5)2xe2x80x94 in which p is a number from 0 to 6 and R5 is hydrogen or C1-C4alkyl
In particularly preferred compounds of the formula (1) Y is a radical of the formula xe2x80x94(CH2)rxe2x80x94, where r is an integer from 1 to 4, or of the formula xe2x80x94(CR5)2xe2x80x94(CR5)2xe2x80x94, in which R5 independently at each occurrence is hydrogen or methyl.
Halogen is preferably chlorine, bromine or fluorine, with particular preference being given to chlorine.
If n or m is 1 the groups R and R1 are preferably in position 4 of the respective benzene ring except when R or R1, respectively, is nitro or COOR5. In this case the group R or R1, respectively, is preferably in position 5.
If n or m is 2 the two R groups or R1 groups are preferably in positions 4 and 6 of the respective benzene ring except when R or R1, respectively, is nitro or COOR5, In this case the two R groups or R1 groups, respectively, are preferably in positions 3 and 5.
If R or R1 is di(C1-C12alkyl)amino the alkyl group can be straight-chain or branched. It preferably contains from 1 to 8, in particular from 1 to 4 and, especially, 1 or 2 carbon atoms.
The radicals R and R1 are preferably hydrogen, nitro, OR5, COOR5 or N(R5)2, with R5 being hydrogen or C1-C4alkyl, especially methyl or ethyl.
The radicals R2 and R3 are especially hydrogen, methyl, ethyl or unsubstituted phenyl.
Aryl is, for example, naphthyl or especially phenyl.
If R6 and R7 together with the nitrogen atom connecting them form a 5-, 6- or 7-membered ring this ring is especially a pyrrolidine, piperidine, morpholine or piperazine ring. The piperazine ring can be substituted, by alkyl, for example, on the nitrogen atom that is not joined to the phenyl radical.
Examples of suitable anions are halide, such as chloride, perchlorate, sulfate, nitrate, hydroxide, BF4xe2x88x92, PF6xe2x88x92, carboxylate, acetate, tosylate and triflate. Preference among these is given to chloride, acetate and carboxylate.
The present invention also provides the compounds of the formula 
in which
n is 0, 1, 2 or 3,
m is 1, 2 or 3,
A is an anion;
Y is a linear or branched alkylene radical of the formula xe2x80x94[C(R5)2]rxe2x80x94, where r is an integer from 1 to 8 and the R5 radicals independently of one another are hydrogen or C1-C4alkyl;
xe2x80x94CXxe2x95x90CXxe2x80x94, in which X is cyano, linear or branched C1-C8alkyl or di(linear or branched C1-C8alkyl)-amino,
xe2x80x94(CH2)qxe2x80x94NR4xe2x80x94(CH2)qxe2x80x94, in which R4 is as defined above and q is 1, 2, 3 or 4; or a 1,2-cyclohexylene radical of the formula: 
xe2x80x83or a 1,2-aryl radical of the formula 
xe2x80x83in which R9 is SO3H, CH2OH or CH2NH2,
R and R1 independently of one another are cyano, halogen, OR5 or COOR5, in which R5 is hydrogen or linear or branched C1-C4alkyl, or are nitro, linear or branched C1-C8alkyl, linear or branched, partially fluorinated or perfluorinated C1-C8alkyl, NHR6 or NR6NR7 in which R6 and R7 are identical or different and are each linear or branched C1-C2alkyl or in which R6 and R7, together with the nitrogen atom connecting them, form a 5-, 6- or 7-membered ring which may include further heteroatoms, or are linear or branched C1-C8alkyl-R6, in which R6 is a radical OR5, COOR5 or NR6NR7 with the above definitions or is NH2, or are xe2x80x94N⊕R4R6R7, in which R4, R6 and R7 are as defined above,
R2 and R3 independently of one another are hydrogen, linear or branched C1-C4 alkyl or unsubstituted aryl, or aryl substituted by cyano, halogen, OR5 or COOR5, in which R5 is hydrogen or linear or branched C1-C4alkyl, or by nitro, linear or branched C1-C8alkyl, NHR5 or NR6R7 in which R6 and R7 are identical or different and are each linear or branched C1-C12alkyl, or in which R6 and R7, together with the nitrogen atom connecting them, form a 5-, 6- or 7-membered ring which may include further heteroatoms, or by linear or branched C1-C8alkyl R6, in which R6 is a radical OR5, COOR5 or NR6R7 with the above definitions or is NH2, or by xe2x80x94N⊕R4R6R7, in which R4, R6 and R7 are as defined above,
with the proviso that R and R1 do not have the same definition if n and m are identical and R2 and R3 are both hydrogen and that, of the radicals R2 and R3, it is not the case that one is hydrogen and the other is phenyl.
The preferred definitions indicated above below the manganese complexes of formula (1) for n, m, Y, A, R, R1, R2 and R3 are also preferred for the compounds of formula (1a).
The compounds of the formula (1) and (1a) are prepared, for example, in a conventional manner from the corresponding ligands and a manganese compound. Preparation processes of this kind are described, for example, in the U.S. Pat. Nos. 5,281,578 and 4,066,459. All of the manganese complexes mentioned therein, however, have symmetrically substituted ligands. Surprisingly, the manganese complexes of the invention, having asymmetric ligands, feature an enhanced specific action as catalysts for oxidations with peroxides.
The ligands of the formula 
in which R, R1, R2, R3, Y, n and m are as defined under the formula (1a) are likewise novel. They are prepared in a conventional manner by, for example, reacting a diamine of the formula H2Nxe2x80x94Yxe2x80x94NH2 first with an aldehyde or ketone of the formula 
and then with an aldehyde or ketone of the formula 
In the formulae (3) and (4) R, R1, R2, R3, n and m are as defined under the formula (1), with the proviso that R and R1 do not have the same definition if n and m are identical.
Of particular interest for use in the process of the invention are the compounds of the formula 
It is also possible to employ the compounds of the formula (1) together with corresponding analogous symmetrical manganese complexes, i.e. with compounds of the formula (1) in which (R)n and (R1)n are identical. Such mixtures are obtained, for example, by reacting a diamine of the formula H2Nxe2x80x94Yxe2x80x94NH2 with a mixture of two different compounds of the formula (3) in the above synthesis of the ligands of the formula (2) and converting the resultant mixture comprising one asymmetric and two symmetrical ligands of the formula (2) into the corresponding Mn complexes.
The present invention additionally provides a detergent comprising
I) 5-90%, preferably 5-70% A) of an anionic surfactant and/or B) of a nonionic surfactant,
II) 5-70%, preferably 5-50% and, in particular, 5-40% C) of a builder substance,
III) 0.1-30%, preferably 1-12% D) of a peroxide, and
IV) 0.005-2%, preferably 0.02-1% and, in particular, 0.1-0.5% E) of a compound of the above-defined formula (1), where the percentages are in each case by weight based on the overall weight of the detergent.
The detergent can be in solid or liquid form as, for example, a nonaqueous liquid detergent comprising not more than 5 and preferably from 0 to 1% by weight of water and as its base may have a suspension of a builder substance in a nonionic surfactant, as described, for example, in GB-A-2,158,454.
Preferably, however, the detergent is in powder or granule form.
This detergent can be prepared, for example, by first preparing an initial powder by spray-drying an aqueous slurry comprising all of the above-mentioned components with the exception of D) and E) and then adding the dry components D) and E) and mixing all of the components with one another.
Alternatively, component E) can be added to an aqueous slurry comprising components A), B) and C) which is then spray-dried, after which component D) can be mixed with the dry mass.
Yet another option is to start from an aqueous slurry which comprises components A) and C) but not, or not all of, component B). The slurry is spray-dried, then component E) is mixed with component B) and added, and, subsequently, component D) is admixed in dry form.
The anionic surfactant A) can be, for example, a sulfate, sulfonate or carboxylate surfactant or a mixture thereof.
Preferred sulfates are those with 12-22 carbon atoms in the alkyl radical, alone or in combination with alkyl ethoxy-sulfates whose alkyl radical has 10-20 carbon atoms. Preferred sulfonates are, for example, alkylbenzenesulfonates with 9-15 carbon atoms in the alkyl radical.
The cation in the anionic surfactants is preferably an alkali metal cation, especially sodium.
Preferred carboxylates are alkali metal sarcosinates of the formula Rxe2x80x94COxe2x80x94N(R1)xe2x80x94CH2COOM1, in which R is alkyl or alkenyl with 8-18 carbon atoms in the alkyl or alkenyl radical, R1 is C1-C4alkyl and M1 is an alkali metal.
The nonionic surfactant B) can be, for example, a condensation product of 3-8 mol of ethylene oxide with 1 mol of primary alcohol having 9-15 carbon atoms.
Examples of suitable builder substances C) are alkali metal phosphates, especially tripolyphosphates, carbonates or bicarbonates, especially their sodium salts, silicates, aluminium silicates, polycarboxylates, polycarboxylic acids, organic phosphonates, aminoalkylenepoly(alkylenephosphonates), or mixtures of these compounds.
Particularly suitable silicates are sodium salts of crystalline phyllosilicates of the formula NaHSltO2t+1.pH2O or Na2SltO2t+1.pH2O, in which t is a number between 1.9 and 4 and p is a number between 0 and 20.
Of the aluminium silicates, preference is given to those obtainable commercially under the names zeolite A, B, X and HS and to mixtures comprising two or more of these components.
Among the polycarboxylates, preference is given to the polyhydroxycarboxylates, especially citrates, and acrylates and also their copolymers with maleic anhydride.
Preferred polycarboxylic acids are nitrilotriacetic add, ethylenediaminetetraacetic acid, and ethylenediaminedisuccinate, both in racemic form and in the enantiomerically pure S,S form.
Particularly suitable phosphonates or aminoalkylenepoly(alkylenephosphonates) are alkali metal salts of 1-hydroxyethane-1,1-diphosphonic acid, nitrilotris(methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid and diethylenetriamine-pentamethylenephosphonic acid.
Suitable peroxide components D) are, for example, the literature-referenced and commercially available organic and inorganic peroxides which bleach textile materials at customary washing temperatures: for example, at from 10 to 95xc2x0 C.
The organic peroxides are, for example, mono- or polyperoxides, especially organic peracids or their salts, such as phthalimidoperoxycaproic acid, peroxybenzoic acid, diperoxydodecanedioic acid, diperoxynonanedioic acid, diperoxydecanedioc acid, diperoxyphthalic acid, or salts thereof.
It is preferred, however, to use inorganic peroxides, examples being persulfates, perborates, percarbonates and persilicates. It is of course also possible to use mixtures of inorganic and/or organic peroxides. The peroxides can be present in different crystal forms and with varying water content and may also be employed together with other organic or inorganic compounds in order to enhance their stability on storage.
Addition of the peroxides to the detergent takes place preferably by mixing the components with the aid, for example, of a screw metering system and/or a fluidized-bed mixer.
In addition to the combination of the invention the detergents may comprise one or more fluorescent whitening agents from the classes, for example, of bistriazinylaminostilbene-disulfonic acid, bistriazolylstilbenedisulfonic acid, bisstyrylbiphenyl or bisbenzofurylbiphenyl, or a bisbenzoxallyl derivative, bisbenzimidazolyl derivative, coumarin derivative or pyrazoline derivative.
In addition, the detergents may comprise soil antiredeposition agents, such as sodium carboxymethylcellulose, pH regulators, such as alkali metal or alkaline earth metal silicates, foam regulators, such as soap, salts for regulating spray drying and granulating properties, such as sodium sulfate, fragrances and, if desired, antistats and fabric softeners, enzymes, such as amylase, bleaches, pigments and/or shading agents. These constituents must of course be stable to the bleach that is employed.
Further preferred additions to the detergents of the invention are polymers which prevent stains due, when washing textiles, to dyes in the wash liquor that have become detached from the textiles under washing conditions. These are preferably polyvinylpyrrolidones, unmodified or modified by incorporation of anionic or cationic substituents, and especially those having a molecular weight in the range from 5000 to 60,000, in particular from 10,000 to 50,000. These polymers are employed preferably in an amount from 0.05 to 5% by weight, in particular from 0.2 to 1.7% by weight, based on the overall weight of the detergent.
In addition, the detergents of the invention may also include what are known as perborate activators, such as TAED or TAGU, for example. Preference is given to TAED, which is employed preferably in an amount from 0.05 to 5% by weight, in particular from 0.2 to 1.7% by weight, based on the overall weight of the detergent.
The examples which follow serve to illustrate the invention without restricting it to them. Parts and percentages are by weight unless specified otherwise.